This project focuses on two general areas. One concerns a continuing exploratory study of new synthetically useful routes to benzoquinones, anneleated hydroquinones, phenols and related aromatic compounds. In general, this methodology involves the ring expansion of 4-alkynyl or 4- arylcyclobutenones, transformations involving initially formed (electrocyclic ring opening) conjugated ketenes. In addition to investigating the synthetic utility and limitations, the mechanism of these rearrangements will also be studied. It is anticipated that these studies will provide useful data to be used in the design of biologically important target compounds and this constitutes the second phase of this study. Specifically, it is anticipated that the convergent nature of the cyclobutenone ring expansion will allow the facile construction of natural products towards the synthesis of natural and unnatural quinones having these structural features deemed necessary for bioreductive alkylating agents and thus compounds of potential use as anticancer agents. Developing a versatile synthesis of the mitomycins will constitute a key objective of this project. Success here will then allow the synthesis of mitomycin analogs as well as compounds related to the nanaomycins, lomazarins, fibrastatin and other potential bioreductive alkylating agents.